EP0006543B1 - Matériel photographique sensible à la lumière, procédé pour sa fabrication ainsi que son utilisation pour la réalisation d'images photographiques - Google Patents

Matériel photographique sensible à la lumière, procédé pour sa fabrication ainsi que son utilisation pour la réalisation d'images photographiques Download PDF

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Publication number
EP0006543B1
EP0006543B1 EP79101945A EP79101945A EP0006543B1 EP 0006543 B1 EP0006543 B1 EP 0006543B1 EP 79101945 A EP79101945 A EP 79101945A EP 79101945 A EP79101945 A EP 79101945A EP 0006543 B1 EP0006543 B1 EP 0006543B1
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EP
European Patent Office
Prior art keywords
silver halide
emulsion
halide emulsion
soluble
iodide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP79101945A
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German (de)
English (en)
Other versions
EP0006543A1 (fr
Inventor
Otto Dr. Lapp
Lothar Dr. Endres
Harold Dr. Hückstädt
Franz Dr. Moll
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Agfa Gevaert AG
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Agfa Gevaert AG
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Publication of EP0006543A1 publication Critical patent/EP0006543A1/fr
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Publication of EP0006543B1 publication Critical patent/EP0006543B1/fr
Expired legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/002—Photosensitive materials containing microcapsules
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03C1/00—Photosensitive materials
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    • G—PHYSICS
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    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G—PHYSICS
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    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/04—Photo-taking processes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0075—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of an heterocyclic ring
    • C09B23/0083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of an heterocyclic ring the heteroring being rhodanine in the chain
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Definitions

  • the invention relates to a light-sensitive photographic material with at least one silver halide emulsion layer, a process for its production and the use for the production of photographic images.
  • the invention relates to a photographic material with an emulsion having a narrow grain size distribution.
  • the silver halide grains are prepared by simultaneously using an aqueous solution of a water-soluble silver salt, e.g. of silver nitrate, and a water soluble halide, e.g. an alkali metal halide such as potassium bromide into a vigorously stirred aqueous solution of a silver halide peptizer, preferably gelatin, a gelatin derivative, or any other protein peptizer.
  • a water-soluble silver salt e.g. of silver nitrate
  • a water soluble halide e.g. an alkali metal halide such as potassium bromide
  • a silver halide peptizer preferably gelatin, a gelatin derivative, or any other protein peptizer.
  • a disadvantage of the process described by Markocki and Romer is that the less soluble emulsions have to be prepared by subjecting part of the Lippmann emulsion used to an Ostwald ripening at an increased bromide ion concentration in order to obtain larger silver halide grains in this way. This naturally results in an emulsion with a heterodisperse particle size distribution.
  • Another serious disadvantage of the The Markocki and Romer method is that it is practically unusable for larger emulsion batches.
  • the Markocki and Romer method can namely be carried out either by continuous or by periodic addition of the Lippmann emulsion to the germ emulsion.
  • the fine-grained component must be added with extraordinarily vigorous stirring in order to avoid the formation of heterodisperse emulsions. This is practically not possible with larger approaches.
  • the Lippmann emulsion is added periodically, there must be considerable pauses between the individual additions in order to avoid the formation of heterodisperse systems. This variant is therefore not suitable for practical use.
  • relatively little iodide is used in both the heavier and the more easily soluble emulsion in the known processes. Thus only emulsions with a relatively low iodide content are obtained.
  • An object of the invention is to provide an improved photographic material with at least one light-sensitive silver halide emulsion layer which is simple to produce compared to known methods and can also have a higher iodide content.
  • Another object of the invention is, in particular, to provide a method with which silver halide emulsions with a narrow grain size distribution can be prepared in a simple manner.
  • DE-C-851 716 discloses silver halide emulsions which are converted using a water-soluble iodide. However, no further silver halide is found on the converted silver halide.
  • An emulsion with a narrow grain size distribution is hereby understood to mean an emulsion in which at least 75% of the silver halide grains lie within a deviation of at most 50% from the mean grain diameter.
  • the silver halide emulsions are monodisperse, with moon-disperse emulsions being understood to mean those in which at least 95% of the silver halide grains lie within a deviation of at most 40% from the mean grain diameter.
  • the emulsion to be treated with the water-soluble iodide can consist entirely or predominantly of silver chloride and / or in particular of silver bromide. However, it can also contain iodide in larger quantities.
  • a solution of a dispersing agent, in particular gelatin, and a certain amount of iodide ions, for example as alkali iodide, are introduced and a Lippmann emulsion with a narrow particle size distribution, which consists predominantly of silver bromide, is added to this solution all at once or gradually , too.
  • a Lippmann emulsion is understood to mean an emulsion whose silver halide grains have a maximum diameter of 0.1 ⁇ . This Lippmann emulsion can be produced by the usual methods, in particular by the double enema method.
  • a silver halide solvent is then added.
  • the Lippmann emulsion serves as its own pre-precipitation.
  • a corresponding proportion of the Lippmann emulsion is converted by the iodide ions present, to which non-converted proportions grow.
  • the silver halide solvent it is also possible to add a portion of the silver halide solvent to the solution of the dispersant and the iodide ions.
  • the average grain diameter of the silver halide grains obtained in this way is preferably between C, 4 .mu.m and 1.5 .mu.m and is controlled by the choice of the transfer conditions for the Lippmann emulsion, in particular by the temperature used and the amount of the silver halide solvent added.
  • a separate pre-precipitation is used.
  • an emulsion with a narrow grain size distribution is first produced, which consists of silver bromide or silver chloride or mixtures thereof. Silver iodide can also be included.
  • emulsions are simplified, for example, by the processes known in emulsion technology or double inlet, possibly pAg-controlled.
  • the precipitate thus produced is treated with an iodide salt solution before or after physical ripening and at least partially converted.
  • the amount of iodide added can be varied within wide limits without causing an undesirable heterodispersity of the precipitation or the finished emulsion.
  • the iodide content of the converted precipitation is preferably between 10 and 100 mol%, based on the silver contained in the precipitation, preferably between 15 and 75 mol%.
  • the converted emulsion is referred to below as a less soluble emulsion.
  • a more soluble, generally fine-grained emulsion preferably a Lippmann emulsion
  • this more soluble emulsion preferably consisting of silver chloride, silver bromide or mixtures thereof and up to about 10 mol% iodide, preferably smaller than 6 moi% iodide.
  • At least one silver halide solvent is added for the process according to the invention.
  • the amount of silver halide solvent used depends on the type of solvent used and the transfer temperature used and can generally be easily determined in a series of experiments. Values between 0.05 and 2 molar are generally achieved.
  • the mixture of the heavier and the more soluble emulsion is digested in the presence of the silver halide solvent until the more soluble emulsion has grown on top of the less soluble emulsion.
  • the ratio of the silver fed in the form of the more readily soluble silver halide emulsion to the silver introduced with the less soluble emulsion is preferably between 0.3: 1 to 30: 1, preferably 1: 1 to 15: 1.
  • at least one of the two emulsions is preferably e.g. desalted and / or concentrated e.g. by flocculation.
  • the flocculated emulsions can be mixed and redispersed together.
  • very high and, in comparison to conventional emulsions, unusual silver concentrations can be set without having to accept the disadvantage of the high salt concentration.
  • the silver concentrations in the redissolution can be between 0.2 to 2 mol of silver per kg of emulsion.
  • the more readily soluble silver halide emulsion can also be added to the less soluble emulsion at different times and in several proportions. Another option is continuous addition.
  • Another embodiment consists of an alternating mode of operation, the conversion and redemption being carried out several times in alternation in succession. In this way, the topographic distribution of the iodide can be done in a targeted and predictable manner.
  • Another possibility is to use several more easily soluble emulsions with different halide contents, which are added successively to the converted, less soluble emulsion. This enables a targeted e.g. gradually adjust iodide gradients.
  • the alternating mode of operation can also be combined with more easily soluble silver halide emulsions of different halide compositions.
  • the transfer parameters such as pAg value, pH value and temperature can be varied within wide limits, the temperature advantageously being chosen between 40 and 80 degrees and the transfer time between 5 and 90 minutes.
  • the pAg is preferably 6.5 to 11.8.
  • Suitable silver halide solvents are: halides, preferably alkali and ammonium halides, in particular bromides or chlorides; Ammonia; Thiocyanates, especially alkali or ammonium thiocyanate; Sulfites, especially alkali or ammonium sulfites; Thiosulfate; organic amines; Thioether, imidazole and imidazole derivatives.
  • organic thioethers are used. Suitable thioethers are described, for example, in US Pat. Nos. 3,271,157, 3,507,657, 3,531,289 and 3574628 and German published patent application 28 24 249.1. Particularly suitable thioethers are also described in German Offenlegungsschrift 2,614,862. Particularly suitable thioethers correspond to the following general formulas:
  • the silver iodide content of the emulsion obtained according to the invention is arbitrary and is preferably between 3 and 15 mol%.
  • hydrophilic film-forming agents are suitable as protective colloid or binder for the silver halide emulsion layer, e.g. Proteins, in particular gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others.
  • Proteins in particular gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others.
  • the layers can also contain other synthetic binders in dissolved or dispersed form, such as homopolymers or copolymers of acrylic or methacrylic acid or their derivatives, such as esters, amides or nitriles, and also vinyl polymers, such as vinyl esters or vinyl ethers.
  • synthetic binders in dissolved or dispersed form, such as homopolymers or copolymers of acrylic or methacrylic acid or their derivatives, such as esters, amides or nitriles, and also vinyl polymers, such as vinyl esters or vinyl ethers.
  • the usual supports can be used for the emulsions according to the invention, e.g. Carriers of cellulose esters such as cellulose acetate or cellulose acetobutyrate, furthermore polyesters, in particular polyethylene terephthalate or polycarbonates, in particular based on bis-phenylolpropane.
  • Carriers of cellulose esters such as cellulose acetate or cellulose acetobutyrate
  • polyesters in particular polyethylene terephthalate or polycarbonates, in particular based on bis-phenylolpropane.
  • paper supports which may contain waterproof polyolefin layers, e.g. made of polyethylene or polypropylene, can also contain supports made of glass or metal.
  • the emulsions can also be chemically sensitized, e.g. by adding sulfur-containing compounds during chemical ripening, for example allyl isothiocyanate, allyl thiourea, sodium thiosulfate and the like.
  • Reducing agents e.g. the tin compounds described in Belgian patents 493,464 or 568,687, also polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, e.g. according to Belgian patent 547 323.
  • Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky, Z.Wiss.Phot. 46, 65-72 (1951).
  • polyalkylene oxide derivatives e.g. with polyethylene oxide with a molecular weight between 1,000 and 20,000
  • condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitols, with alkyl-substituted phenolines, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides The condensation products have a molecular weight of at least 700, preferably more than 1,000.
  • these sensitizers can of course be used in combination, as described in Belgian patent 537 278 and British patent 727 982.
  • the emulsions can also be optically sensitized, e.g. with the usual polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
  • polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
  • sensitizers are described in F. M. Hamer's work "The Cyanine Dyes and Related Compounds", 1964, Interscience Publishers, John Wiley and Sons.
  • the emulsions can contain the usual stabilizers, e.g. homeopolar or salt-like compounds of mercury with aromatic or heterocyclic rings such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • stabilizers e.g. homeopolar or salt-like compounds of mercury with aromatic or heterocyclic rings such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • azaindenes preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are in the article by Birr, Z.Wiss.Phot. 47 (1952), 2-58.
  • Other suitable stabilizers include heterocyclic mercapto compounds, e.g. Phenyl mercaptotetrazole, quaternary benzothiazole derivatives and benzotriazole.
  • the emulsions can be hardened in the usual manner, for example with formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
  • formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
  • the photographic layers can be hardened with hardeners of the epoxy type, the heterocyclic ethylene imine or the acryloyl type.
  • hardeners are e.g. in German laid-open specification 2 263 602 or in British patent specification 1 266 655.
  • hardeners of the diazine, triazine or 1,2-dihydroquinoline series are alkyl or arylsulfony group-containing diazine derivatives, derivatives of hydrogenated diazines or triazines, e.g. 1,3,5-hexahydrotriazine, fluorine-substituted diazine derivatives, such as e.g.
  • Fluoropyrimidine esters of 2-substituted 1,2-dihydroquinoline or 1,2-dihydroisoquinoline-N-carboxylic acids.
  • Vinyl sulfonic acid hardeners, carbodiimide or carbamoyl hardeners such as e.g. in German laid-open publications 2 263 602, 2 225 230 and 1 808 685, French patent 1 491 807, German patent 872 153 and GDR patent 7218.
  • Other useful hardeners are described, for example, in British Patent 1,268,550.
  • the present invention can be used for both black and white and colored pho graphic images can be applied.
  • Colored photographic images can be produced, for example, according to the known principle of chromogenic development in the presence of color couplers which react with the oxidation product of coloring p-phenylenediamine developers to form dyes.
  • the color couplers can, for example, be added to the color developer according to the principle of the so-called development process.
  • the photographic material itself contains the usual color couplers, which are usually incorporated into the silver halide layers.
  • the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or a-naphthol type.
  • the thoroughly sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or imidazolone type usually being used.
  • the blue-sensitive layer can contain, for example, a non-diffusing color coupler for generating the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
  • Color couplers of this type are known in large numbers and are described in a large number of patents. Examples include the publication "Farbkuppler” by W. Pelz in “Mitanderen aus der Anlagen Anlagenslaboratorien der Agfa, Leverkusen / Ober", Volume 111 (1961) and K. Venkataraman in "The Chemistry of Synthetic Dyes", Vol. 4, 341 -387, Academic Press, 1971.
  • 2-equivalent couplers can be used as further non-diffusing color couplers; these contain a removable substituent in the coupling point, so that they only require two equivalents of silver halide to form the color, in contrast to the usual 4-equivalent couplers.
  • the 2-equivalent couplers that can be used include, for example, the known DIR couplers in which the cleavable residue is released as a diffusing development inhibitor after reaction with color developer oxidation products.
  • the so-called white couplers can also be used to improve the properties of the photographic material.
  • the non-diffusing color couplers and coloring compounds are added to the light-sensitive silver halide emulsions or other casting solutions by customary known methods. If the compounds are soluble in water or alkali, they can be added to the emulsions in the form of aqueous solutions, optionally with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide. Insofar as the non-diffusing color couplers and coloring compounds are water- or alkali-insoluble compounds, they can be emulsified in a known manner, e.g.
  • the emulsions prepared according to the invention can be used in a wide variety of ways. They can be used for the production of negative photographic materials but also for the production of photographic materials with unveiled, direct positive silver halide emulsions, i.e. Those that have a relatively high sensitivity to the inner grain without superficial veil and that are developed under obscuring conditions.
  • the emulsions according to the invention can be used for color instant image processes or color transfer processes in a manner known per se.
  • the dyes for the partial color images diffuse into an image-receiving layer, where they are firmly anchored, or the color couplers diffuse into the image-receiving layer, where they are converted into the image dye after customary color development.
  • Color transfer processes and used in such processes Couplers are also described in U.S. Patents 2,983,606, 3,807,817, 3,185,567, 3,227,550, 3,227,551, 3,227,552, 3,227,554, 3,253,915, 3,415,644, 3,415,645 and 3,415,646 described.,
  • the emulsions according to the invention can also be used for dye transfer processes in which a diffusion-resistant compound is present in the respective layer, which is a dye or a dye precursor and which, when developed in the presence of the 'alkaline processing composition, under the action of imagewise formed oxidation products of photographic Developers cleaving diffusing dyes, preferably containing acid groups.
  • a diffusion-resistant compound is present in the respective layer, which is a dye or a dye precursor and which, when developed in the presence of the 'alkaline processing composition, under the action of imagewise formed oxidation products of photographic Developers cleaving diffusing dyes, preferably containing acid groups.
  • Diffusion-resistant coloring substances according to US Pat. No. 3,628,952, for example, are particularly suitable. These compounds split off diffusible dyes during the reaction with oxidation products from black and white or color developers.
  • Another useful class of compounds is described in German Patent 1,095,115. The compounds mentioned here give diffusible dyes, which generally belong to the class of azomethine dyes, in the reaction with oxidized color developer.
  • Another useful coloring system is described in U.S. Patents 3,443,939 and 3,443,940. In this system, diffusible dyes are split off under the action of oxidized developer substances with the formation of a ring.
  • the photographic materials according to the invention are therefore outstandingly suitable for the production of photographic images by imagewise exposure, development and customary further processing.
  • the materials according to the invention are distinguished by the fact that they have at least one silver halide emulsion with a narrow grain size distribution and any and in particular higher iodide contents.
  • the emulsions produced according to the invention have a high inhibibility and are therefore particularly suitable for achieving high interimage effects.
  • the interimage effect is usually used to improve the sensitometric properties of photographic materials and is described, for example, in the corresponding article by C. R. Barr in "Photographic Science and Engineering” 13 (1969), page 74 ff.
  • a Lippmann emulsion is prepared according to the method specified by W. Markocki (Korpuluskar Photographie, IV (1963), page 165) with the modification that no cadmium nitrate is used.
  • the grains of the Lippmann emulsion have an average grain diameter of 0.07 ⁇ .
  • 1500 g of the Lippmann emulsion obtained with the amount of silver halide corresponding to 340 g of silver nitrate are added at 45 ° C. in the course of 10 minutes to a solution of 22.5 g of potassium iodide and 120 g of gelatin containing inhibitors and maturing bodies in 5 l of distilled water.
  • the Lippman emulsion After the Lippman emulsion has been converted by the iodide ions, 375 ml of a 14.7 molar ammonia solution are added. After a digestion time of 30 minutes at 45 ° C., the emulsion is cooled in a known manner and adjusted to pH 5.0 with dilute sulfuric acid. The emulsion is then coagulated in a known manner, washed and finally redispersed in a known manner with the addition of water and gelatin of the type mentioned above at a pH of 6.5 and then chemically sensitized with a gold rhodanide complex salt by a customary method. For ripening, the mixture is digested at a temperature of 53 ° C. and then phenol is added in a conventional manner for preservation.
  • the emulsion obtained has a narrow grain size distribution, the mean grain diameter being ⁇ , 58 ⁇ .
  • Figure 1 shows the so-called cumulative frequency curve for these emulsions. Each point on the ordinate of this curve indicates what percentage of the crystals are larger than the abscissa value to be assigned.
  • a sample of the emulsion is poured onto a suitable carrier, 20 ml of 1% strength aqueous solution of 4-hydroxy-6-methyl-1,3,3a, 7 being applied to each kg of the emulsion samples before the casting -tetraazainden 35 ml of 7.5% aqueous solution of saponin and 35 ml of 2% aqueous solution of mucochloric acid are added.
  • the photographic material obtained is imagewise exposed in the usual way through a gray wedge and developed at 20 ° C. for 7 minutes in the following developer:
  • Example 1 To prepare an emulsion, the procedure is the same as that given in Example 1, except that only 750 g of the Lippmann emulsion specified is added to the solution of potassium iodide and gelatin in 5 liters of distilled water. The emulsion obtained is processed in the same manner as in Example 1.
  • Figure 2 shows the cumulative frequency curve of the emulsion obtained, with an average grain diameter of 0.65 ⁇ . The sensitometric values after exposure and processing according to Example 1 are shown in Table 1.
  • the emulsion is poured onto a cellulose acetate base (silver coating, calculated as AgNO 3 ; 3.7 g / m 2 ).
  • the material After drying and exposure behind a step wedge and a suitable filter in a sensitometer, the material is developed in the following developer for 3 1/4 minutes at 38 ° C:
  • Figure 3 shows the density curves obtained. It can be seen that the emulsion reacts in a pronounced manner to the stabilizer split off by the DIR ⁇ coupler.
  • Table 2 shows the sensitometric data.
  • a silver chloride / bromide emulsion with 52 mol% bromide is prepared according to the information provided by Glafkides (P. Glafkides Photographic Chemistry Fountain Press p. 341 and ff. 1958), so that the average grain size is 0.35 ⁇ .
  • 12 mol% iodide, based on the precipitated silver halide, in the form of a 10% aqueous potassium iodide solution is slowly added to the emulsion and digested.
  • the emulsion is cooled, flocculated and washed.
  • the flocculate is then redispersed again.
  • the emulsion thus prepared contains 1.1 mol of silver halide per kg.
  • the gelatin-silver ratio is 0.3.
  • the solution is then cooled, flocculated, washed and redispersed.
  • the emulsion contains 1, 3 mol of silver halide per kg.
  • the iodide content of the emulsion is 6 mol%.
  • a gelatin solution, thiosulphate and gold salts are added to the emulsion, heated to 54 ° C and chemically ripened.
  • the finished emulsion has a gelatin / silver ratio of 1.0.
  • the emulsion is mixed with 35 mg triazinedolizine and 200 mg saponin, poured onto a carrier made of acetyl cellulose and developed in the developer specified in Example 1. A medium-sensitive fine-grained emulsion is obtained.
  • an ammoniacal silver bromide / iodide emulsion with 3 mol% iodide is produced.
  • 19 mol% of iodide in the form of a 10% aqueous potassium iodide solution are added to the emulsion, based on the precipitated silver halide.
  • Spherical halosilver grains of very uniform grain size are obtained, the mean grain diameter being approximately 0.55 ⁇ .
  • the emulsion is flocked and washed and redispersed.
  • the emulsion contains 1.1 mol of silver halide / kg.
  • the gelatin-silver ratio is 0.35.
  • the emulsion is flocculated, washed, redispersed, and brought to a gelatin-silver ratio of 1, the 0th It is matured in a known manner with sulfur-gold ripening to the maximum sensitivity.
  • the finished emulsion is mixed with triazaindolizine and saponin and poured onto a carrier made of acetyl cellulose. Formalin is also added to the protective layer. The layers are exposed and developed as in Example 4. A high sensitivity with fine grain is obtained. The emulsion shows a very high contrast.
  • a bromoiodosilver emulsion with a narrow particle size distribution with 6 mol% iodide is produced in a double jet process.
  • the grain size is 0.18 ⁇ .
  • 42 mol% of iodide, based on the precipitated silver halide, is added to the emulsion in the form of an aqueous potassium iodide solution.
  • the emulsion is then flocculated, washed and redispersed.
  • the emulsion contains 1.4 mol of silver halide per kg. 500 ml of water, 75 g of NHQBr and 1500 ml of a 7% methionine solution are added to the redispersed emulsion. 9.8 mol of an AgBr-Lippmann emulsion are added to this emulsion within 5 minutes.

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Claims (10)

1. Matériau photographique sensible à la lumière comportant au moins une couche d'émulsion d'halogénure d'argent de granulométrie étroite contenant de l'iodure, qui a été préparée à partir d'une émulsion d'halogénure d'argent de départ avec un iodure soluble dans l'eau avec conversion au moins partielle, ledit procédé étant caractérisé en ce qu'il contient une couche d'halogénure d'argenf dont l'emulsion d'halogénure d'argent de départ convertie a été mûrie en présence d'un solvant de l'halogénure d'argent, éventuellement avec une nouvelle addition d'émulsion d'halogénure d'argent qui est plus soluble que l'émulsion d'halogénure d'argent de départ convertie, jusqu'à ce que les fractions d'émulsion plus facilement solubles aient grossi sur les fractions d'émulsion d'halogénure d'argent de départ converties.
2. Matériau selon la revendication 1, caractérisé en ce que l'emulsion de départ contient au moins 10 moles % d'iodure d'argent.
3. Matériau selon la revendication 1, caractérisé en ce qu'au moins 75% en poids des grains d'halogénure d'argent de l'émulsion d'halogénure d'argent finale ont un diamètre qui ne s'écarte pas de plus de 50% du diamètre moyen.
4. Matériau selon la revendication 1, caractérisé en ce qu'il contient des coupleurs chromogènes. _
5. Matériau selon la revendication 1, caractérisé en ce que l'émulsion d'halogénure d'argent de départ a un diamètre moyen de grain de 0,1 µ au maximum.
6. Matériau selon la revendication 1, caractérisé en ce qu'on utilise une émulsion d'halogénure d'argent pour la préparation de laquelle on a concentré et/ou déminéralisé l'émulsion de départ convertie ou l'émulsion plus soluble ajoutée avant l'addition de l'émulsion plus soluble.
7. Matériau selon la revendication 1, caractérisé en ce que le rapport molaire de l'argent introduit sous forme de l'emulsion plus soluble à l'argent introduit sous forme de l'émulsion de départ convertie est comprise entre 0,3:1 et 30:1.
8. Matériau selon la revendication 1, caractérisé en ce qu'il contient une couche d'émulsion d'halogénure d'argent dans laquelle la conversion, éventuellement l'addition d'émulsion d'halogénure d'argent plus soluble et la maturation s'effectuent l'une après l'autre plus d'une fois.
9. Procédé pour la préparation d'un matériau photographique sensible à la lumière par application sur un support de couche d'une couche d'émulsion d'halogénure d'argent contenant de l'iodure, de granulométrie étroite, qui a été préparée par conversion au moins partielle à partir d'une émulsion d'halogénure d'argent de départ avec un iodure soluble dans l'eau, ledit procédé étant caractérisé en ce que l'emulsion d'halogenure d'argent de départ convertie a été mûrie en présence d'un solvant de l'halogénure d'argent éventuellement avec addition supplémentaire d'émulsion d'halogénure d'argent qui est pius tacilement soluble que l'émulsion d'halogénure djargent de départ convertie, jusqu'à ce que les fractions de l'émulsion plus solubles aient grossi sur les fractions d'émulsion d'halogénure d'argent de départ converties.
10. Utilisation du matériau selon la revendication 1, pour la production d'image photographique par exposition suivant une image et développement.
EP79101945A 1978-06-27 1979-06-15 Matériel photographique sensible à la lumière, procédé pour sa fabrication ainsi que son utilisation pour la réalisation d'images photographiques Expired EP0006543B1 (fr)

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DE2932650C2 (de) * 1979-08-11 1982-03-11 Du Pont de Nemours (Deutschland) GmbH, 4000 Düsseldorf Verfahren zur Herstellung einer monodispersen photographischen Silberhalogenidemulsion
JPS58100847A (ja) * 1981-12-12 1983-06-15 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラー写真感光材料
JPS5910947A (ja) * 1982-07-10 1984-01-20 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料
DE3404854A1 (de) * 1984-02-11 1985-08-14 Agfa-Gevaert Ag, 5090 Leverkusen Fotografisches aufzeichnungsmaterial
JPS625234A (ja) * 1985-07-01 1987-01-12 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
JPS62168139A (ja) * 1986-01-20 1987-07-24 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
EP0312959B1 (fr) * 1987-10-16 1992-08-05 Fuji Photo Film Co., Ltd. Emulsion photographique à l'halogénure d'argent
GB8916042D0 (en) * 1989-07-13 1989-08-31 Kodak Ltd Process of preparing a tabular grain silver bromoiodide emulsion and emulsions produced thereby
US5254453A (en) * 1992-04-16 1993-10-19 Eastman Kodak Company Process for preparing narrow size distribution small tabular grains
DE4233714A1 (de) * 1992-10-07 1994-04-14 Agfa Gevaert Ag Verfahren zur Herstellung von Silberhalogenidemulsionen
JP2603189B2 (ja) * 1993-10-27 1997-04-23 コニカ株式会社 感光性ハロゲン化銀乳剤

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US3046134A (en) * 1958-12-12 1962-07-24 Eastman Kodak Co Sensitization of photographic silver halide emulsions with polymeric compounds containing a plurality of sulfur atoms
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EP0006543A1 (fr) 1980-01-09
JPS5536892A (en) 1980-03-14

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